US4316737A - 2-Phenyl-5,6-dihydro-4-pyrone derivatives and herbicidal compositions in which they are present - Google Patents

2-Phenyl-5,6-dihydro-4-pyrone derivatives and herbicidal compositions in which they are present Download PDF

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Publication number
US4316737A
US4316737A US06/015,626 US1562679A US4316737A US 4316737 A US4316737 A US 4316737A US 1562679 A US1562679 A US 1562679A US 4316737 A US4316737 A US 4316737A
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US
United States
Prior art keywords
sub
compound according
carbons
dihydro
pyrone
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Expired - Lifetime
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US06/015,626
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English (en)
Inventor
Francois Guigues
Gilles Peris Y Saborit
Guy Borrod
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Bayer CropScience SA
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Philagro SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/74—Benzo[b]pyrans, hydrogenated in the carbocyclic ring

Definitions

  • the invention relates to new 2-phenyl-5,6-dihydro-4-pyrone derivatives and to the herbicidal compositions in which they are present.
  • R 1 and R 2 which are identical or different, each represent an atom or radical chosen from amongst the hydrogen atom and alkyl radicals containing from 1 to 4 carbon atoms, or together form an alkylene chain containing from 2 to 6 carbon atoms
  • R 3 represents an alkyl radical containing from 1 to 4 carbon atoms, an alkenyl radical containing from 2 to 4 carbon atoms, an alkynyl radical containing from 2 to 4 carbon atoms, a halogenoalkyl radical containing from 1 to 4 carbon atoms or an alkoxyalkyl radical containing from 3 to 5 carbon atoms
  • Y represents an atom or radical chosen from amongst halogen atoms, alkyl radicals containing from 1 to 4 carbon atoms and alkoxy radicals containing from 1 to 4 carbon atoms
  • n represents an integer which can be equal to 1, 2 or 3. When n is equal to 2 or 3,
  • R 1 and R 2 each represent an alkyl radical
  • the compound of the formula I can exist in the form of two diastereoisomers of which one has the cis configuration and the other has the trans configuration. These diastereoisomers, of which the levels of herbicidal activity can be different, form part of the present invention.
  • the invention relates more particularly to the compounds corresponding to the formula: ##STR3## in which R 1 , R 2 , R 3 and Y have the same meaning as in the formula I and n' represents an integer equal to 0, 1 or 2.
  • the compounds according to the invention can be prepared in accordance with a process comprising the following three steps:
  • the reaction is carried out in an anhydrous, inert organic medium, such as e.g. benzene, toluene, xylene or ethyl ether, by bringing the reactants into contact at a temperature between about 0° and 100° C. and then by heating the reaction mixture at a temperature between about 35° and 150° C. (e.g. by heating under reflux) until the reaction is complete.
  • an anhydrous, inert organic medium such as e.g. benzene, toluene, xylene or ethyl ether
  • Magnesium ethylate is preferably used as the magnesium alcoholate and can be prepared in situ by reacting magnesium with ethanol in an anhydrous, inert organic medium, in the presence of carbon tetrachloride.
  • reaction is carried out in an anhydrous, inert organic medium, such as ethyl ether, toluene or benzene, at a temperature between about 0° and 20° C. Under these conditions, the equilibrium between the compound V and its enol form VI is strongly displaced in favour of the formation of the latter compound.
  • an anhydrous, inert organic medium such as ethyl ether, toluene or benzene
  • This reaction is carried out by first treating the reaction mixture, comprising the compound VI and the compound of the formula R 4 OMgCl, with a dilute aqueous solution of a strong acid, such as sulphuric acid, at a temperature between 0° and 20° C., this causing a partial cyclisation of the compound VI and the decomposition, by hydrolysis, of the compound of the formula R 4 OMgCl, and by then treating the compound VI, which is partially cyclised and has been separated off beforehand, with a dilute, anhydrous alcoholic solution of a strong acid, such as hydrochloric acid, at a temperature between about 60° and 100° C., the said acid optionally being prepared in situ.
  • a strong acid such as sulphuric acid
  • anhydrous, dilute ethanolic solution of hydrochloric acid which is prepared in situ by the action of a small amount of acetyl chloride on ethanol, is preferably used.
  • the resulting compound of the formula I is then purified by the customary methods, such as recrystallisation, molecular distillation, liquid phase chromatography or the like.
  • the process is preferably carried out using an acetic acid derivative corresponding to the formula: ##STR12## in which R 3 , Y and n have the same meaning as in the formula I, and an acid chloride of the formula: ##STR13## in which R 1 and R 2 have the same meaning as in the formula I.
  • NMR nuclear magnetic resonance spectrometry
  • Magnesium ethylate (9.1 g, 0.08 mol), dry toluene (50 ml) and ethyl 4-fluorobenzoylacetate (16.8 g, 0.08 mol) are mixed at ambient temperature and then heated under reflux for one hour and cooled to about 5° C. with a bath of ice-cooled water.
  • Hydroquinone (0.1 g) is added and 2-ethylacryloyl chloride (9.5 g, 0.08 mol) is then run in at a temperature between 0° and 10°.
  • dry acetonitrile (30 ml) is added in order to render the medium fluid.
  • reaction mixture is then stirred for one hour at ambient temperature and poured onto a mixture of ice (50 g) and concentrated sulphuric acid (5 ml).
  • the organic phase is then decanted and the aqueous phase is extracted with toluene.
  • the combined organic phases are washed with 10% strength H 2 SO 4 , then with 5% strength NaHCO 3 solution and then with water and are finally dried and concentrated.
  • Fine magnesium turnings (1.9 g), absolute ethanol (12 ml), dry benzene (50 ml) and dry carbon tetrachloride (0.4 ml) are heated to 50°-60° C., whilst stirring gently. When the evolution of hydrogen slows down, the mixture is heated under reflux for 1 hour and cooled to ambient temperature.
  • Ethyl 4-fluorobenzoylacetate (16.8 g, 0.08 mol) is then run in and the mixture is heated under reflux for one hour and then cooled to about 5° C.
  • Acetonitrile 50 ml is then added in order to render the medium fluid and trans-2-methylbut-2-enoyl chloride (9.5 g, 0.08 mol) is run in dropwise. The mixture is then stirred for one hour at ambient temperature.
  • the liquid obtained is taken up in 95° proof ethanol (200 ml) and acetyl chloride (0.5 ml) and the mixture is heated under reflux for half an hour.
  • the oily residue (21,5 g) is slowly crystallised, and then rectrystallised from a mixture (200 ml) of 2 parts of hexane and one part of cyclohexane.
  • this compound consists of a mixture of isomers comprising 95% by weight of the trans isomer and 5% by weight of the cis isomer.
  • trans isomer which melts at 75° C., can be isolated by recrystallisation from cyclohexane of the mixture of isomers obtained previously.
  • the cis isomer which melts at 85.2° C., can be isolated, from the mother liquors resulting from the recrystallisation of the mixture of isomers obtained previously, by preparative liquid chromatography, using the following eluting mixture: 2,2,4-trimethylpentane (95%)/isopropan-2-ol (5%).
  • a number of seeds are sown in 9 ⁇ 9 ⁇ 9 cm pots filled with light agricultural earth, this number being determined as a function of the plant species and the size of the seed.
  • the seeds are then covered with an approximately 3 mm thick layer of earth.
  • the pots are treated by spraying each pot with an amount of spraying mixture which corresponds to a volume of 500 liters/hectare and contains the active ingredient at the relevant dose.
  • the spraying mixture is prepared by diluting, with water, an emulsifiable concentrate having the following composition by weight:
  • the treated pots are then placed in troughs which are intended to receive the moistening water, by subirrigation, and are kept for 35 days at ambient temperature under 70% relative humidity.
  • the compounds according to the invention exhibit an excellent herbicidal activity towards a large number of both graminaceous and dicotyledon adventitious plants.
  • This herbicidal activity occurs in accordance with a particular mode of action by causing, in the sensitive plant species, albinism phenomena accompanied by a rapid slowing down of the growth of the plants and/or by their drying out, and finally by their destruction.
  • the dose of active ingredient to be used can vary from 0.25 to 8 kg/hectare depending on the compound used, the type of crop and the nature of the soil. This dose is preferably between 0.5 and 5 kg/hectare.
  • compositions which generally comprise, in addition to the active ingredient according to the invention, a carrier and/or a surface-active agent, and in which the proportion of active ingredient generally remains between 0.01% and 95% by weight.
  • carrier denotes an organic or inorganic, natural or synthetic material with which the active ingredient is combined in order to facilitate its application to the plant, to seeds or to the soil, or in order to facilitate its transportation or handling.
  • the carrier can be solid (clays, natural or synthetic silicates, resins, waxes, solid fertilisers or the like) or fluid (water, alcohols, ketones, a petroleum fraction, chlorohydrocarbons or liquefied gases).
  • the surface-active agent can be an emulsifier, dispersing agent or wetting agent, each of which can be ionic of non-ionic. Examples which may be mentioned are salts of polyacrylic acids and of ligninsulphonic acids, and products resulting from the condensation of ethylene oxide with fatty alcohols, fatty acids or fatty amines.
  • compositions according to the invention can be prepared in the form of wettable powders, dusting powders, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.
  • the wettable powders are usually prepared so that they contain from 20to 95% by weight of active ingredient, and they usually contain, in addition to a solid carrier, from 0 to 5% by weight of a wetting agent and from 3 to 10% by weight of one or more stabilisers and/or other additives such as penetrating agents, adhesives or anti-caking agents, dyestuffs and the like.
  • a wettable powder is given:
  • the granules which are intended to be placed on the soil, are usually prepared so that they have dimensions of between 0.1 and 2 mm, and they can be manufactured by agglomeration or impregnation.
  • the granules will contain from 0.5 to 25% of active ingredient and from 0 to 10% by weight of additives such as stabilisers, slowrelease modifiers, binders and solvents.
  • the emulsifiable concentrates which can be applied by spraying usually contain, in addition to the solvent and where necessary, a co-solvent, from 10 to 50% by weight/volume of active ingredient and from 2 to 20% by weight/volume of suitable additives such as stabilisers, penetrating agents, corrosion inhibitors and dyestuffs and adhesives.
  • composition of an emulsifiable concentrate is given, the amounts being expressed in g/litre:
  • the suspension concentrates which can also be applied by spraying, are prepared so as to give a stable fluid product which does not form a deposit, and they usually contain from 10 to 75% by weight of active ingredient, from 0.5 to 15% by weight of surface-active agents, from 0.1 to 10% by weight of thixotropic agents, from 0 to 10% by weight of suitable additives such as anti-foam agents, corrosion inhibitors, stabilisers, penetrating agents and adhesives, and, as the carrier, water or an organic liquid in which the active ingredient is essentially insoluble; certain organic solid materials or inorganic salts can be dissolved in the carrier to assist in preventing sedimentation or to act as anti-freeze agents for the water.
  • Aqueous dispersions and aqueous emulsions e.g. compositions obtained by diluting, with water, a wettable powder or an emulsifiable concentrate according to the invention, fall within the general scope of the present invention.
  • the emulsions can be of the water-in-oil type or of the oil-in-water type and they can have a thick consistency such as that of a "mayonnaise".
  • composition according to the invention can contain other ingredients, e.g. protective colloids, adhesives or thickeners, thixotropic agents, stabilisers or sequestering agents, as well as other known active ingredients having pesticidal properties, in particular insecticidal or fungicidal properties.
  • protective colloids e.g. protective colloids, adhesives or thickeners, thixotropic agents, stabilisers or sequestering agents, as well as other known active ingredients having pesticidal properties, in particular insecticidal or fungicidal properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US06/015,626 1978-03-15 1979-02-27 2-Phenyl-5,6-dihydro-4-pyrone derivatives and herbicidal compositions in which they are present Expired - Lifetime US4316737A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7808228 1978-03-15
FR7808228A FR2419940A1 (fr) 1978-03-15 1978-03-15 Nouveaux derives de la phenyl-2 dihydro-5,6 pyrone-4 et compositions herbicides les contenant

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US4316737A true US4316737A (en) 1982-02-23

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US06/015,626 Expired - Lifetime US4316737A (en) 1978-03-15 1979-02-27 2-Phenyl-5,6-dihydro-4-pyrone derivatives and herbicidal compositions in which they are present

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Country Link
US (1) US4316737A (cs)
JP (1) JPS54130574A (cs)
AR (1) AR222325A1 (cs)
AT (1) AT364834B (cs)
AU (1) AU522783B2 (cs)
BE (1) BE874842A (cs)
BR (1) BR7901577A (cs)
CA (1) CA1134373A (cs)
CH (1) CH637950A5 (cs)
CS (1) CS208490B2 (cs)
CU (1) CU21127A3 (cs)
DD (1) DD142277A5 (cs)
DE (1) DE2910283A1 (cs)
DK (1) DK105079A (cs)
EG (1) EG13621A (cs)
ES (1) ES478604A1 (cs)
FR (1) FR2419940A1 (cs)
GB (1) GB2016463B (cs)
GR (1) GR68032B (cs)
HU (1) HU182561B (cs)
IE (1) IE47866B1 (cs)
IL (1) IL56841A (cs)
IT (1) IT1166693B (cs)
LU (1) LU81042A1 (cs)
NL (1) NL7901970A (cs)
NZ (1) NZ189889A (cs)
OA (1) OA06219A (cs)
PH (1) PH14037A (cs)
PL (1) PL120343B1 (cs)
PT (1) PT69350A (cs)
RO (2) RO76884A (cs)
SE (1) SE7902355L (cs)
SU (1) SU919595A3 (cs)
TR (1) TR20004A (cs)
YU (1) YU62479A (cs)
ZA (1) ZA791182B (cs)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4383849A (en) * 1980-11-14 1983-05-17 Rhone-Poulenc Agrochimie 2,3-Dihydro-4-pyrone derivatives, their preparation the herbicidal compositions in which they are present and their use for selectively destroying weeds in crops
US4460400A (en) * 1981-06-03 1984-07-17 Ciba-Geigy Corporation Dihydropyrones, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds
US4812160A (en) * 1986-01-11 1989-03-14 Basf Aktiengesellschaft Cyclohexenone derivatives, preparation and use thereof as herbicides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493586A (en) * 1969-01-23 1970-02-03 Dow Chemical Co 3-(beta-aryl-beta-(arylthio) (or arylseleno)-propionyl)pyrone products
US3989737A (en) * 1973-12-24 1976-11-02 Nippon Soda Company Limited 2-Cyclohexene-1-one derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3493586A (en) * 1969-01-23 1970-02-03 Dow Chemical Co 3-(beta-aryl-beta-(arylthio) (or arylseleno)-propionyl)pyrone products
US3989737A (en) * 1973-12-24 1976-11-02 Nippon Soda Company Limited 2-Cyclohexene-1-one derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Gelin et al., Bull. Soc. Chim. de France, (1968), No. 1, pp. 288-298. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4383849A (en) * 1980-11-14 1983-05-17 Rhone-Poulenc Agrochimie 2,3-Dihydro-4-pyrone derivatives, their preparation the herbicidal compositions in which they are present and their use for selectively destroying weeds in crops
US4460400A (en) * 1981-06-03 1984-07-17 Ciba-Geigy Corporation Dihydropyrones, novel starting products used therein, compositions containing the novel dihydropyrones as active ingredients, and the use thereof for combating weeds
US4812160A (en) * 1986-01-11 1989-03-14 Basf Aktiengesellschaft Cyclohexenone derivatives, preparation and use thereof as herbicides
US5074903A (en) * 1986-01-11 1991-12-24 Basf Aktiengesellschaft Cyclohexenone derivatives, preparation and use thereof as herbicides

Also Published As

Publication number Publication date
IE790606L (en) 1979-09-15
NZ189889A (en) 1980-05-08
TR20004A (tr) 1980-06-10
AR222325A1 (es) 1981-05-15
IE47866B1 (en) 1984-07-11
GB2016463A (en) 1979-09-26
FR2419940B1 (cs) 1980-09-05
SU919595A3 (ru) 1982-04-07
FR2419940A1 (fr) 1979-10-12
SE7902355L (sv) 1979-09-16
IT1166693B (it) 1987-05-06
IL56841A (en) 1982-07-30
IT7920977A0 (it) 1979-03-14
DK105079A (da) 1979-09-16
HU182561B (en) 1984-02-28
CS208490B2 (en) 1981-09-15
IL56841A0 (en) 1979-05-31
YU62479A (en) 1983-02-28
DD142277A5 (de) 1980-06-18
PT69350A (fr) 1979-04-01
RO76884A (ro) 1981-08-17
BE874842A (fr) 1979-09-14
RO82007B (ro) 1983-05-30
CU21127A3 (es) 1988-02-15
GB2016463B (en) 1982-06-03
AU522783B2 (en) 1982-06-24
PH14037A (en) 1980-12-12
CH637950A5 (fr) 1983-08-31
CU21127A (es) 1981-12-04
AT364834B (de) 1981-11-25
DE2910283A1 (de) 1979-10-04
NL7901970A (nl) 1979-09-18
GR68032B (cs) 1981-10-27
OA06219A (fr) 1981-09-30
JPS54130574A (en) 1979-10-09
RO82007A (ro) 1983-06-01
AU4508179A (en) 1979-09-20
BR7901577A (pt) 1979-10-16
PL214111A1 (cs) 1980-03-10
ATA193179A (de) 1981-04-15
EG13621A (en) 1983-12-31
PL120343B1 (en) 1982-02-27
ES478604A1 (es) 1979-06-01
LU81042A1 (fr) 1980-09-24
CA1134373A (en) 1982-10-26
ZA791182B (en) 1980-03-26

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